1

Analytical and Bioanalytical Chemistry

Electronic Supplementary Material

Optimization and comparison of several extraction methods for

determining perfluoroalkyl substances in abiotic environmental solid

matrices using liquid chromatography-mass spectrometry

María Lorenzo, Julián Campo, Yolanda Picó

2

Table S1 Family, structure, name, acronym, CAS number and formula of PFASs

Family

(acronym) Structure n Name Acronym CAS number Formula

Perfluoroalkyl carboxylic acids

(PFCAs) CnF2n+1COOH

3 Perfluorobutanoic acid PFBA 375-22-4 C4HF7O2

5 Perfluorohexanoic acid PFHxA 307-24-4 C6HF11O2

6 Perfluoroheptanoic acid PFHpA 375-85-9 C7HF13O2

7 Perfluorooctanoic acid PFOA 335-67-1 C8HF15O2

8 Perfluorononanoic acid PFNA 375-95-1 C9HF17O2

8 Perfluoro-7-methyloctanoic acid ipPFNA Not available C9HF17O2

9 Perfluorodecanoic acid PFDA 335-76-2 C10HF19O2

10 Perfluoroundecanoic acid PFUnDA 2058-94-8 C11HF21O2

11 Perfluorododecanoic acid PFDoDA 307-55-1 C12HF23O2

12 Perfluorotridecanoic acid PFTrDA 72629-94-8 C13HF25O2

13 Perfluorotetradecanoic acid PFTeDA 376-06-7 C14HF27O2

15 Perfluorohexadecanoic acid PFHxDA 67905-19-5 C16HF31O2

17 Perfluorooctadecanoic acid PFODA 16517-11-6 C18HF35O2

Perfluoroalkane sulfonic acids

(PFSAs)

CnF2n+1SO3X

X = Na, K

4 Potassium perfluorobutanesulfonate PFBS 29420-49-3 C4F9SO3K

6 Sodium perfluorohexanesulfonate PFHxS 82382-12-5 C6F13SO3Na

7 Sodium perfluoroheptanesulfonate PFHpS Not available C7F15SO3Na

8 Sodium perfluorooctanesulfonate PFOS 1763-23-1 C8F17SO3Na

9 Sodium perfluoro-7-methyloctanesulfonate ipPFNS Not available C9F19SO3Na

10 Sodium perfluorodecanesulfonate PFDS Not available C10F21SO3Na

Fluorotelomer unsaturated

carboxylic acids

(FTUCAs)

CnF2n+1CF=CHCOOH 7 2H-Perfluoro-2-decenoic acid FOUEA 70887-84-2 C10H2F16O2

Table S2 Molecular structures of PFASs

Acronym

PFBA

PFHxA

PFHpA

PFOA

PFNA

ipPFNA

PFDA

PFUnDA

PFDoDA

PFTrDA

Molecular structures of PFASs

Structure

3

Table S2 (continued) Molecular structures of PFASs

Acronym

PFTeDA

PFHxDA

PFODA

PFBS

PFHxS

PFHpS

PFOS

ipPFNS

PFDS

FOUEA

Made with ChemBioOffice Ultra 14.0

Molecular structures of PFASs

Structure

Made with ChemBioOffice Ultra 14.0

4

5

Table S3 Name, acronym and formula of MPFASs

Name Acronym Formula

Perfluoro-n-(1,2,3,413

C4)butanoic acid MPFBA 13

C4HF7O2

Perfluoro-n-(1,2-13

C2)hexanoic acid MPFHxA 13

C212

C4HF11O2

Sodium perfluoro-1-hexane(18

O2)sulfonate MPFHxS C6F13S18

O216

ONa

Perfluoro-n-(1,2,3,4-13

C4)octanoic acid MPFOA 13

C412

C4HF15O2

Sodium perfluoro-1-(1,2,3,4-13

C4)octanesulfonate MPFOS 13

C412

C4F17SO3Na

Perfluoro-n-(1,2,3,4,513

C5)nonanoic acid MPFNA 13

C512

C4HF17O2

Perfluoro-n-(1,213

C2)decanoic acid MPFDA 13

C212

C8HF19O2

Perfluoro-n-(1,213

C2)undecanoic acid MPFUnDA 13

C212

C9HF21O2

Perfluoro-n-(1,213

C2)dodecanoic acid MPFDoDA 13

C212

C10HF23O2

6

Table S4 Coordinates of all sampling points

Point UTM X(a)

UTM Y(a)

Reference

Segura

River

Sampling

1 688383 4216632 Bridge, Benejúzar

2 690974 4217731 Azud de Alfeitamí, Almoradí

3 692415 4218261 After WWTP, Algorfa

4 696728 4217353 Stand near Formentera

5 700024 4218173 Rojales

6 703132 4218850 Bridge, Guardamar

Turia

River

Sampling

(2012)

12-1 673997 4398936 Calles

12-2 674589 4397963 Calles

12-3 679648 4392454 Near Loriguilla dam

12-4 682877 4388118 Fuencaliente

12-5 690376 4386376 Bugarra

12-6 692308 4386783 Bugarra

12-7 691432 4386786 Bugarra

12-8 713610 4377916 La Presa

12-9 717215 4375932 Manises

12-10 671242 4497930 Villalba Alta

12-11 671242 4497930 Villalba Alta

12-12 667500 4488337 Near Alfambra

12-13 620809 4475013 Before Tramacastilla

12-14 622144 4476231 After Tramacastilla

12-15 642173 4474094 After Gea de Albarracín

12-16 654549 4468794 Near San Blas

12-17 660388 4467562 Teruel

12-18 659446 4468617 Near Parador, Teruel

12-19 646939 4435616 Ademúz

12-20 661820 4403623 Before Benagéber dam

12-21 661622 4400225 Benagéber dam

Turia

River

Sampling

(2013)

13-1 682877 4388118 Fuencaliente

13-2 674403 4398751 Calles

13-3 679298 4392436 Chulilla

13-4 682877 4388118 Chulilla

13-5 690584 4386265 Bugarra

13-6 692308 4386783 Bugarra

13-7 717246 4376190 Orchard, Huerto S. Francisco

13-8 713585 4377967 Orchard, La Presa

13-9 711326 4379920 Orchard, Masía de Traver

13-10 722638 4370253 Orchard, Faitanar

13-11 726201 4363485 Orchard L’Albufera

13-12 728582 4366902 Orchard, L’Arbre del Gos

13-13 728023 4369884 Orchard, Montolivet

13-14 671584 4498215 Villalba Alta-Alfambra

13-15 667504 4488313 Villalba Alta-Alfambra

13-16 620779 4475005 Tramacastilla

7

Table S4 (continued) Coordinates of all sampling points

Point UTM X(a)

UTM Y(a)

Reference

Turia

River

Sampling

(2013)

13-17 622151 4476223 Tramacastilla

13-18 642150 4474127 Gea de Albarracín

13-19 654762 4468671 Vega de Teruel

13-20 659446 4468596 Vega de Teruel

13-21 659683 4464556 Vega de Teruel

13-22 618967 4480511 Tramacastilla

13-23 626270 4474757 Tramacastilla

13-24 661825 4471198 Vega de Teruel

13-25 659043 4463240 Vega de Teruel

13-26 662818 4401283 Benagéber dam

(a) UTM coordinates in ETRS89

Figure S1a Turia River sampling (2012). Made with gvSIG 2.0

12-20 12-21

12-19

12-4 12-3

12-13

12-14 12-15 12-16

12-1 12-2

12-7

12-5 1

Valencia

Cuenca

Teruel

12-10 y 12-11

12-18

12-17

12-12

ling (2012). Made with gvSIG 2.0 Figure S1b Turia River sampling (2013). Made with gvSIG 2.0

12-9 12-8 7

12-6

13

13-13-22 13-17

13-16 13-23

13-18

13-19

13-20 13-24

13-21

13-25

13-26 13

13

13

Valencia

Cuenca

Castellón

Teruel

11

8 ing (2013). Made with gvSIG 2.0

13-14

-15

21 25

13-2

13-3 13-1

13-4

13-5 13-6

13-11 13-12

13-10 13-13

13-9

13-8

13-7

Valencia

Castellón

9

Table S5 Instrumental characteristics used for PFASs determination

LC CONDITIONS

Analytical column Kinetex XB-C18: 50.0 × 2.1 mm, 1.7 μm particle size (Phenomenex,

Torrance, USA)

Column temperature 30° C

Volume injected 5 μL

Mobile phase (A) Water – (B) methanol both with 10 mM Ammonium Formate

Flow rate 0.2 mL min-1

Linear gradient 0 min (30 % B), 0.5 min (30 % B), 12 min (95 % B), 20 min (95 % B),

and return to the initial conditions (equilibration time 12 min)

TRIPLE QUADRUPOLE MS/MS CONDITIONS

Ionization characteristics

and source

MS/MS performed in selected reaction monitoring mode (SRM)

with electrospray ionization (ESI) in negative mode

Gas temperature 300° C

Gas flow 11 L min-1

Nebulizer 30 psi

Capillary voltage 4000 V

Chamber current 1.27 μA

Scan type MRM, with MS1 and MS2 at unit resolution and cell acceleration

voltage of 7 eV

10

Table S6 Dynamic MRM conditions for LC-MS/MS determination of PFASs

(a)

PFASs(a)

tR (b)

(min) Precursor

ion MS1

(c) Frag

(d) (V) CE

(e) (V) MS2

(f) Frag (V) CE (V)

MS2/MS1 (%)

(%RSD)(g)

MPFBA 1.9 217 172 62 0 - - - -

PFBA 2.3 213 169 66 5 - - - -

PFBS 8.4 299 99 142 38 80 142 26 15.3 (2.3)

PFHxA 11.1 313 269 71 5 119 71 5 10.6 (3.3)

MPFHxA 11.2 315 270 71 5 119 71 5 7.1 (0.8)

PFHpA 12.7 363 319 76 5 169 76 5 68.5 (9.2)

PFHxS 12.8 399 99 169 37 80 169 29 65.9 (10.8)

MPFHxS 12.8 403 103 164 33 84 164 37 23.5 (4.3)

PFOA 13.6 413 369 87 5 169 87 5 46.7 (1.4)

MPFOA 13.6 417 372 82 5 169 82 13 22.5 (0.6)

PFHpS 13.7 449 99 179 37 80 179 57 31.9 (8.9)

ipPFNA 14.2 463 419 87 5 169 87 5 27.0 (1.2)

PFOS 14.3 499 99 190 41 80 190 65 82.2 (3.2)

PFNA 14.4 463 419 82 5 219 82 5 13.2 (0.9)

MPFNA 14.4 468 423 82 5 223 82 9 17.6 (1.4)

11

Table S6 (continued) Dynamic MRM conditions for LC-MS/MS determination of PFASs

PFASs(a)

tR (b)

(min) Precursor

ion MS1

(c) Frag

(d) (V) CE

(e) (V) MS2

(f) Frag (V) CE (V)

MS2/MS1 (%)

(%RSD)(g)

MPFOS 14.4 503 99 180 41 80 180 61 30.0 (1.1)

FOUEA 14.6 457 393 167 9 - - - -

ipPFNS 14.8 549 99 195 45 80 195 73 21.6 (1.6)

PFDA 15.0 513 469 89 5 269 89 13 15.3 (2.2)

MPFDA 15.0 515 470 92 5 270 92 12 8.4 (0.4)

PFUnDA 15.5 563 519 104 5 269 104 13 14.1 (0.6)

MPFUnDA 15.5 565 520 94 5 269 94 13 4.3 (0.4)

PFDS 15.5 599 99 80 80 80 80 80 17.6 (1.3)

PFDoDA 16.0 613 569 94 5 269 94 13 9.0 (0.8)

MPFDoDA 16.0 615 570 112 5 - - - -

PFTrDA 16.4 663 619 104 0 169 104 24 8.1 (1.8)

PFTeDA 16.8 713 669 112 5 169 112 25 7.8 (0.2)

PFHxDA 17.6 813 769 114 8 169 114 28 9.6 (1.1)

PFODA 18.4 913 869 134 10 169 128 29 13.3 (1.1)

(a) Compounds ordered by retention time; (b) tR = retention time; (c) MS1 = selected product ion for quantification; (d) Frag = fragmentor; (e) CE =

collision energy; (f) MS2 = selected product ion for qualification; (g) MS2 /MS1 (%RSD) = = mean values obtained from the matrix-matched calibration

curves and relative standard deviation of the ratio. Italics mean isotopically labelled internal standard

12

Table S7 Characteristics of selected soil and sediment for method validation

Characteristics Soil Sediment

Organic matter (%) 4.29 2.78

Water content (%) 1.80 1.54

Carbonates (%) 22.74 28.25

pH (ClK) 7.35 7.25

Electrical conductivity (dS m-1

) 0.81 -

Nitrogen (cmolc kg-1

) 23.46 -

Sodium (cmolc kg-1

) 0.05 0.04

Potassium (cmolc kg-1

) 0.42 0.30

Magnesium (cmolc kg-1

) 2.18 1.21

Calcium (cmolc kg-1

) 10.55 14.25

Cation-exchange capacity (cmolc kg-1

) 13.21 15.75

Clay (%) 13.97 26.30

Silt (%) 14.68

Sand (%) 71.34 73.70

13

Table S8 Parameters for instrumental validation

Family

(acronym) Compound R

2

LOD

(ng mL-1

)

LOQ

(ng mL-1

)

Repeatability

RSD (%)

Reproducibility

RSD (%)

Perfluoroalkyl carboxylic acids

(PFCAs)

PFBA 0.9923 1.11 3.33 1.1 3.1

PFHxA 0.9942 0.28 0.83 4.4 9.1

PFHpA 0.9926 0.28 0.83 6 12.0

PFOA 0.9963 0.28 0.83 5.4 7.1

PFNA 0.9950 0.56 1.67 0.2 0.6

ipPFNA 0.9953 0.56 1.67 6.9 10.7

PFDA 0.9989 0.28 0.83 2.7 4.8

PFUnDA 0.9939 0.56 1.67 0.1 0.6

PFDoDA 0.9965 0.11 0.33 2.9 5.3

PFTrDA 0.9992 0.11 0.33 8.4 10.1

PFTeDA 0.9909 0.28 0.83 7.4 9.5

PFHxDA 0.9900 0.56 1.67 2.6 3.5

PFODA 0.9871 1.11 3.33 1.2 2.3

Perfluoroalkane sulfonic acids

(PFSAs)

PFBS 0.9920 1.11 3.33 0.1 0.1

PFHxS 0.9946 0.56 1.67 1.6 3.8

PFHpS 0.9956 0.11 0.33 9.6 11.4

PFOS 0.9953 1.11 3.33 3.8 5.0

ipPFNS 0.9982 1.11 3.33 6.9 10.8

PFDS 0.9927 0.28 0.83 0.9 1.6

Fluorotelomer unsaturated carboxylic acids

(FTUCAs) FOUEA 0.9902 1.11 3.33 0.5 1.6

14

Table S9 PFAS concentrations (ng g-1

) in sediment samples from the Segura River

Compound Point 1 Point 2 Point 3 Point 4 Point 5 Point 6

PFCAs

PFBA 14.91 13.95 5.60 14.38 9.69 4.27

PFHxA n.d. n.d. n.d. n.d. n.d. n.d.

PFHpA n.d. n.d. n.d. n.d. n.d. n.d.

PFOA 0.57 n.d. 0.07 n.d. n.d. 0.31

PFNA n.d. n.d. n.d. n.d. n.d. n.d.

ipPFNA n.d. n.d. n.d. n.d. n.d. n.d.

PFDA n.d. n.d. n.d. n.d. n.d. n.d.

PFUnDA n.d. n.d. n.d. n.d. n.d. n.d.

PFDoDA n.d. n.d. n.d. n.d. n.d. n.d.

PFTrDA n.d. 0.39 n.d. n.d. n.d. n.d.

PFTeDA n.d. 1.05 n.d. n.d. n.d. n.d.

PFHxDA n.d. n.d. n.d. n.d. n.d. n.d.

PFODA n.d. n.d. n.d. n.d. n.d. n.d.

PFSAs

PFBS n.d. n.d. n.d. n.d. n.d. n.d.

PFHxS n.d. n.d. n.d. n.d. n.d. n.d.

PFHpS n.d. n.d. n.d. n.d. n.d. n.d.

PFOS 1.45 0.85 1.17 2.29 0.88 0.86

ipPFNS n.d. n.d. n.d. n.d. n.d. n.d.

PFDS n.d. n.d. n.d. n.d. n.d. n.d.

FTUCAs

FOUEA n.d. n.d. n.d. n.d. n.d. 2.56

n.d. = not detected

15

Table S10 PFAS concentrations (ng g-1

) in soil samples from the Turia River during year 2012

Compound 12-1 12-2 12-3 12-4 12-5 12-6 12-7 12-8 12-9 12-10

PFCAs

PFBA 2.78 1.07 14.81 9.55 4.72 17.96 2.75 16.63 1.68 9.18

PFHxA <LOQ n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.

PFHpA n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.

PFOA 0.19 0.07 <LOQ n.d. n.d. 0.10 0.89 0.57 1.16 0.13

PFNA n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.

ipPFNA n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.

PFDA n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.

PFUnDA n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.

PFDoDA n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.

PFTrDA n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.

PFTeDA n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.

PFHxDA n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.

PFODA n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.

PFSAs

PFBS n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.

PFHxS n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.

PFHpS n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.

PFOS 0.82 n.d. n.d. n.d. n.d. n.d. n.d. n.d. 1.03 n.d.

ipPFNS n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.

PFDS n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.

FTUCAs

FOUEA n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.

n.d. = not detected

<LOQ = below limit of quantification

16

Table S10 (continued) PFAS concentrations (ng g-1

) in soil samples from the Turia River during year 2012

Compound 12-11 12-12 12-13 12-14 12-15 12-16 12-17 12-18 12-19 12-20 12-21

PFCAs

PFBA n.d. 1.31 11.55 1.05 n.d. 7.22 6.24 3.19 4.61 n.d. n.d.

PFHxA n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.

PFHpA n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.

PFOA n.d. n.d. n.d. 2.00 0.09 0.15 n.d. 1.65 n.d. 3.08 n.d.

PFNA n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.

ipPFNA n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.

PFDA n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.

PFUnDA n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.

PFDoDA n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.

PFTrDA n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.

PFTeDA n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.

PFHxDA n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.

PFODA n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.

PFSAs

PFBS n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.

PFHxS n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.

PFHpS n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.

PFOS n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. 2.74 n.d. n.d.

ipPFNS n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.

PFDS n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.

FTUCAs

FOUEA n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.

n.d. = not detected

17

Table S11 PFAS concentrations (ng g-1

) in soil samples from the Turia River during year 2013

Compound 13-1 13-2 13-3 13-4 13-5 13-6 13-7 13-8 13-9 13-10 13-11 13-12 13-13

PFCAs

PFBA n.d. n.d. n.d. n.d. 1.38 2.81 4.49 n.d. n.d. n.d. n.d. 1.15 6.18

PFHxA n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.

PFHpA n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.

PFOA n.d. 0.06 n.d. n.d. n.d. n.d. 0.16 n.d. n.d. n.d. 0.76 3.43 n.d.

PFNA n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.

ipPFNA n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.

PFDA n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.

PFUnDA n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.

PFDoDA n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.

PFTrDA n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.

PFTeDA n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.

PFHxDA n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.

PFODA n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.

PFSAs

PFBS n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.

PFHxS n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.

PFHpS n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.

PFOS n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. 1.81 0.69 4.15 3.48

ipPFNS n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.

PFDS n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.

FTUCAs

FOUEA n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.

n.d. = not detected

18

Table S11 (continued) PFAS concentrations (ng g-1

) in soil samples from the Turia River during year 2013

Compound 13-14 13-15 13-16 13-17 13-18 13-19 13-20 13-21 13-22 13-23 13-24 13-25 13-26

PFCAs

PFBA n.d. n.d. n.d. n.d. 1.88 n.d. n.d. 64.04 17.84 n.d. 1.50 2.07 7.82

PFHxA n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.

PFHpA n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.

PFOA n.d. n.d. n.d. n.d. 1.96 n.d. n.d. 6.96 n.d. n.d. 0.10 6.33 n.d.

PFNA n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.

ipPFNA n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.

PFDA n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.

PFUnDA n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.

PFDoDA n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.

PFTrDA n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.

PFTeDA n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.

PFHxDA n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.

PFODA n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.

PFSAs

PFBS n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.

PFHxS n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.

PFHpS n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.

PFOS n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.

ipPFNS n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.

PFDS n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.

FTUCAs

FOUEA n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d.

n.d. = not detected